CN111398385A - Composite electrode for heavy metal ion detection and preparation method thereof - Google Patents
Composite electrode for heavy metal ion detection and preparation method thereof Download PDFInfo
- Publication number
- CN111398385A CN111398385A CN202010389232.6A CN202010389232A CN111398385A CN 111398385 A CN111398385 A CN 111398385A CN 202010389232 A CN202010389232 A CN 202010389232A CN 111398385 A CN111398385 A CN 111398385A
- Authority
- CN
- China
- Prior art keywords
- vermiculite
- bismuth
- electrode
- heavy metal
- composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 78
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 55
- 238000001514 detection method Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims description 16
- 229910052902 vermiculite Inorganic materials 0.000 claims abstract description 85
- 239000010455 vermiculite Substances 0.000 claims abstract description 85
- 235000019354 vermiculite Nutrition 0.000 claims abstract description 85
- 239000000243 solution Substances 0.000 claims abstract description 66
- 229920000767 polyaniline Polymers 0.000 claims abstract description 60
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 59
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 59
- 150000002500 ions Chemical class 0.000 claims abstract description 42
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical class CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910021397 glassy carbon Inorganic materials 0.000 claims abstract description 35
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- 238000012360 testing method Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 239000003607 modifier Substances 0.000 claims abstract description 6
- 238000003968 anodic stripping voltammetry Methods 0.000 claims abstract description 5
- 239000012224 working solution Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 30
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 235000010413 sodium alginate Nutrition 0.000 claims description 14
- 229940005550 sodium alginate Drugs 0.000 claims description 14
- 239000000661 sodium alginate Substances 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 150000001621 bismuth Chemical class 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000012417 linear regression Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical group [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 14
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 229910001451 bismuth ion Inorganic materials 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000003575 carbonaceous material Substances 0.000 description 16
- 229910000416 bismuth oxide Inorganic materials 0.000 description 15
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000000835 electrochemical detection Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000007853 buffer solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
Abstract
The invention discloses a composite electrode for detecting heavy metal ions; the composite electrode is prepared by taking bismuth composite vermiculite loaded polyaniline carbide as a modifier and modified sodium alginate as a film-forming agent to modify a glassy carbon electrode on the surface; the method specifically comprises the following steps: (1) adsorbing bismuth ions by vermiculite with physical adsorption, polymerizing polyaniline on the surface in situ, and roasting at a gradient temperature to obtain bismuth composite vermiculite loaded polyaniline carbide; (2) dispersing bismuth composite vermiculite loaded polyaniline carbide in modified sodium alginate dispersion liquid and coating the dispersion liquid on the surface of a polished glassy carbon electrode to prepare a composite electrode; the composite electrode is used as a working electrode, can be used for electrochemically detecting heavy metal lead and cadmium ions, takes a solution containing the heavy metal ions as a working solution, and adopts an anodic stripping voltammetry to test the concentration of the heavy metal ions; can simultaneously detect the concentration of lead and cadmium ions, and shows higher sensitivity, wide detection range and lower detection limit.
Description
Technical Field
The invention relates to the field of electrode material preparation, in particular to a composite electrode for heavy metal ion detection and a preparation method thereof.
Background
Heavy metals pose a significant threat to human health and survival invisibly due to concealment, nondegradation and long-term accumulation, heavy metal detection in drinking water, food, medicine and the like is widely concerned, at present, heavy metal detection methods mainly comprise atomic absorption, atomic fluorescence, inductively coupled plasma-mass spectrometry and the like, but the methods usually need to use a precise large instrument and carry out complicated operations such as special treatment on a sample, so that the cost is high, and real-time, on-site and convenient and rapid detection cannot be carried out; the electrochemical detection is popular because of the advantages of convenient operation, high detection sensitivity, rapid detection and the like; the selection of the electrode in the electrochemical detection can obviously influence the detection sensitivity and the enrichment effect on heavy metals so as to influence the detection limit; at present, a working electrode of an electrochemical sensor for heavy metal detection is usually a glassy carbon electrode, but the sensitivity is not high, and with the continuous maturity of a chemical modification electrode technology, a glassy carbon electrode is usually subjected to surface modification to obtain an electrode with high detection sensitivity, low detection limit and wide application range;
bismuth has special physical and chemical properties, so that bismuth-based electrodes are widely concerned in the field of detection of heavy metals, the conventional preparation method of bismuth-based electrodes mostly adopts a form of depositing a bismuth film or bismuth oxide on the surface of the electrodes in situ or ex situ, and bismuth film deposition needs to strictly control the conditions of bismuth ion concentration, solution pH, deposition potential and the like during deposition, so that the bismuth film deposition process is complicated, and the electrode preparation process is complicated; in addition, the phenomenon of bismuth nanoparticle agglomeration or bismuth film over-thickness caused by unreasonable condition control can reduce the detection sensitivity and the utilization rate of the bismuth film; meanwhile, the problems of poor stability and low reproducibility of the electrode caused by the falling of the bismuth film exist;
at present, with the increasing maturity of electrochemical sensor technology, electrochemical sensors for heavy metal detection are widely researched; however, the traditional electrochemical sensor for detecting heavy metals has a complex preparation process and low detection sensitivity, and substances modified on the surface of the sensor can only generate specific signals for specific molecules, and cannot meet the requirement of simultaneously detecting multiple heavy metal ions, so that research and development of working electrodes of the electrochemical sensor with detection capability for multiple heavy metals are urgently needed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a composite electrode for heavy metal ion detection; the composite electrode is prepared by taking bismuth composite vermiculite loaded polyaniline carbide as a modifier and modified sodium alginate as a film-forming agent to modify a glassy carbon electrode on the surface; the electrode is used as a working electrode, a solution containing heavy metal ions is used as a working solution, and the concentration of the heavy metal ions is tested by adopting an anodic stripping voltammetry method; the concentration of lead and cadmium ions can be detected simultaneously, and the detection of the lead and/or cadmium ions shows higher sensitivity, wide detection range and lower detection limit;
in order to achieve the purpose, the technical scheme of the invention is as follows:
a composite electrode for detecting heavy metal ions is prepared by taking bismuth composite vermiculite loaded polyaniline carbide as a modifier and modified sodium alginate as a film-forming agent to modify a glassy carbon electrode on the surface, and specifically comprises the following steps:
(1) preparing bismuth composite vermiculite loaded polyaniline carbide:
(1-1) vermiculite pretreatment: the vermiculite powder is soaked in bismuth salt reducing sugar solution for ultrasonic treatment for 12 to 24 hours after being washed with water, acid, water and dried in sequence; filtering and drying to obtain bismuth composite vermiculite;
(1-2) dissolving aniline in an acid solution to form an acid solution of aniline, dispersing the bismuth composite vermiculite powder in the step (1-1) in the acid solution, uniformly stirring, adding hydrogen peroxide into the acid solution, stirring and reacting at 25-30 ℃ for 20-25 hours to obtain paste, removing the solvent from the paste, and placing the paste in a tubular furnace to roast to obtain bismuth composite vermiculite loaded carbonized polyaniline;
(2) preparing a modified sodium alginate dispersion liquid:
adding polyol into a sodium alginate solution, stirring and dispersing uniformly, then dropwise adding a silane coupling agent into the solution under the stirring condition of 50-60 ℃, and reacting for 3-5 hours to obtain a modified sodium alginate dispersion solution for later use;
(3) preparation of composite electrode
Grinding the vermiculite loaded carbonized polyaniline powder in the step (1), dispersing the grinded powder in the modified sodium alginate dispersion liquid in the step (2), coating the grinded powder on the surface of the glassy carbon electrode, immersing the coated glassy carbon electrode into a calcium ion solution for crosslinking, and drying to obtain the bismuth composite vermiculite loaded carbonized polyaniline modified glassy carbon electrode;
preferably, the particle size of the vermiculite powder in the step (1-1) is 200-400 meshes, and the acid washing is soaking treatment by using 5 mol/L HCl solution which is 2-5 times of the weight of the vermiculite;
preferably, the bismuth salt in the step (1-1) is one of bismuth nitrate, bismuth acetate and bismuth chloride, the molar concentration of the bismuth salt in the bismuth salt reducing sugar solution is 0.02-0.04 mol/L, the molar ratio of the bismuth salt to the reducing sugar is 1: 1, and the addition amount of the bismuth salt solution is 2-4 times of the weight of the vermiculite;
preferably, the acid in the step (1-2) is hydrochloric acid or sulfuric acid, and the concentration of the acid solution is 1-5 mol/L;
preferably, the concentration of the aniline in the acid solution in the step (1-2) is 0.5-1 mol/L, the mass ratio of the added vermiculite powder to the aniline acid solution is 1: 10-20, and the molar ratio of the aniline to the hydrogen peroxide is 1: 2-2: 1;
preferably, the roasting process in the step (1-2) is carried out in three stages, wherein the roasting temperature in the first stage is 200-300 ℃, and the roasting time is 1-2 h; the second stage is roasting at 500-;
preferably, the concentration of the sodium alginate in the step (2) is 1 to 4 weight percent, and the polyhydric alcohol pentaerythritol; the additive amount of the pentaerythritol accounts for 8-10% of the weight of the sodium alginate; the adding amount of the silane coupling agent is 10-15% of the mass of the sodium alginate;
preferably, the silane coupling agent is an aminosilane coupling agent;
the invention also provides a method for electrochemically detecting heavy metal ions, which comprises the steps of taking the prepared bismuth composite vermiculite loaded polyaniline carbide modified glassy carbon electrode as a working electrode, taking a solution containing heavy metal ions as a working solution, adopting anodic stripping voltammetry test for testing, constructing a linear regression equation according to the relation between the concentration of the heavy metal ions and peak current, and calculating the concentration of the heavy metal ions in the solution to be tested; the heavy metal ions are lead ions and/or cadmium ions;
the bismuth composite vermiculite loads carbonized polyaniline modified glassy carbon electrode; vermiculite is a natural nontoxic lamellar mineral, has a higher layer charge number, a higher cation exchange capacity and a stronger adsorption capacity; bismuth ions are uniformly loaded on the surface of vermiculite through ion exchange, electrostatic action or physical adsorption, then polyaniline is polymerized in situ on the surface of the vermiculite, and then is roasted at high temperature, and the vermiculite expands to form a nano-scale layered structure and capillary pores in the roasting process, so that sufficient loading space is provided for bismuth oxide and polyaniline carbide; the dispersibility and stability of the bismuth oxide and the carbon material are improved; the stacking and agglomeration of bismuth oxide and carbon materials are effectively avoided; meanwhile, the polyaniline forms nitrogen-doped carbon materials with a net structure in the roasting process to uniformly cover the layers of the vermiculite, so that the vermiculite is endowed with the electric conductivity; the process of expanding and layering the vermiculite, the deposition of the bismuth oxide and the carbonization of the polyaniline are completed in one step, so that the preparation process is simplified, and the dispersibility and stability of the bismuth oxide and the carbon material are effectively improved; the electrode material has higher electron transmission capability and heavy metal enrichment capability, and is beneficial to electrochemical detection;
the N-doped carbon material with a net-shaped porous structure is obtained after the polyaniline is carbonized, and lone-pair electrons on nitrogen atoms can play a role of current carriers, so that the nitrogen-doped carbon material has good conductivity; meanwhile, the N-doped carbon material obtained by adopting a temperature programming mode has higher specific surface area, and is beneficial to increasing the enrichment amount of heavy metals;
pentaerythritol is added in the preparation process of the mercapto-modified sodium alginate, the pentaerythritol reacts with a silane coupling agent to obtain inorganic cage polysilsesquioxane taking the pentaerythritol as a skeleton core, the inorganic cage polysilsesquioxane and the sodium alginate are connected through dehydration condensation or a hydrogen bond action to form sodium alginate sol with good mechanical strength, the stability of a sodium alginate coating film is ensured, a pure glassy carbon electrode is easy to damage, the bismuth composite vermiculite loaded carbonized polyaniline is coated on the surface of the glassy carbon electrode by taking the modified sodium alginate as a film forming agent, the dropping of the bismuth composite vermiculite loaded carbonized polyaniline is avoided, and the stability, the acid and alkali corrosion resistance and the like of the glassy carbon electrode can be effectively improved.
Advantageous effects
The composite electrode disclosed by the invention is simple in preparation process, low in cost, environment-friendly, easy to operate, low in detection limit and high in test speed, can be used for monitoring heavy metal ions in real time, can be used for simultaneously measuring the concentrations of lead ions and cadmium ions in a solution, and has wide application prospects;
the composite electrode has good electron transmission capability and heavy metal enrichment capability, effectively improves the sensitivity of electrochemical detection, and shows wide detection range and low detection limit; the composite electrode of the invention has the characteristics of high stability and good reproducibility.
The vermiculite is used as a carrier of the bismuth oxide and the polyaniline carbide, and the lamellar structure of the vermiculite can effectively prevent the bismuth oxide and the polyaniline carbide from falling off, avoid agglomeration and separation in the use process, and effectively improve the stability of the bismuth oxide and the carbon material, so that the stability of the electrode is improved; the carbonized polyaniline is uniformly covered on the surface of the vermiculite, so that the conductivity of the vermiculite is improved, the stability and water solubility of the carbon material are improved by the vermiculite, and the enrichment amount of metal ions is increased; in addition, the vermiculite has the capacity of adsorbing and storing far infrared rays, so that the surface energy of the electrode surface is enhanced, the activity of active sites on the electrode surface is enhanced, and the detection sensitivity is improved;
the formed vermiculite loaded carbonized polyaniline is dispersed in modified sodium alginate and coated on the surface of a glassy carbon electrode, and the modified sodium alginate plays a role in stabilizing the glassy carbon electrode; on the other hand, the film-forming agent has good water absorption capacity and heavy metal adsorption capacity as a good film-forming agent, effectively improves the enrichment of heavy metal ions on the surface of the electrode, shortens the detection time, enables the electrode to respond in a short time, improves the detection sensitivity of a solution with lower heavy metal ion concentration, and reduces the detection limit.
Drawings
FIG. 1 is an SEM image of a bismuth-loaded polyaniline carbide composite vermiculite;
FIG. 2 is N of bismuth-compounded vermiculite-supported polyaniline carbide (prepared in example 1 and comparative example 2) according to the present invention2Adsorption and desorption curves;
FIG. 3 is a linear relationship curve of lead ion and cadmium ion elution peak current and concentration;
Detailed Description
Example 1
A composite electrode for detecting heavy metal ions is prepared by taking bismuth composite vermiculite loaded polyaniline carbide as a modifier and modified sodium alginate as a film-forming agent to modify a glassy carbon electrode on the surface, and specifically comprises the following steps:
(1) preparing bismuth composite vermiculite loaded polyaniline carbide:
(1-1) pretreating vermiculite, namely sequentially carrying out water washing, acid washing, water washing and drying on 10g of 400-mesh vermiculite powder with the particle size of 200-;
(1-2) dissolving 0.05mol of aniline in 100ml of 1 mol/L hydrochloric acid solution, dispersing 1g of bismuth composite vermiculite powder in the solution, stirring the solution uniformly, adding 0.1mol of hydrogen peroxide into the solution, stirring the solution at 25 ℃ for reaction for 25 hours to obtain paste, removing the solvent of the paste, putting the paste in a tube furnace, introducing nitrogen for 30 minutes, heating the mixture to 200 ℃ at the speed of 4 ℃/min, roasting the mixture for 2 hours, heating the mixture to 500 ℃ for 2 hours, heating the mixture to 800 ℃ for roasting the mixture for 2 hours, and cooling the mixture to obtain bismuth composite vermiculite loaded carbonized polyaniline;
(2) preparing a modified sodium alginate dispersion liquid:
taking 100g of 1wt% sodium alginate solution, dropwise adding 0.8g of pentaerythritol into the 1wt% sodium alginate solution, stirring and dispersing uniformly, dropwise adding 1g of aminopropyltrimethoxysilane into the solution under the stirring condition at 50 ℃, and reacting for 5 hours to obtain modified sodium alginate dispersion for later use;
(3) preparation of working electrode
Grinding the vermiculite loaded carbonized polyaniline powder in the step (1), dispersing the grinded powder in the modified sodium alginate dispersion liquid in the step (2), coating the grinded powder on the surface of a polished glassy carbon electrode, immersing the coated glassy carbon electrode into 100m L0.5 mol/L calcium ion solution for crosslinking, and drying to obtain a bismuth composite vermiculite loaded carbonized polyaniline modified glassy carbon electrode;
example 2
A composite electrode for detecting heavy metal ions is prepared by taking bismuth composite vermiculite loaded polyaniline carbide as a modifier and modified sodium alginate as a film-forming agent to modify a glassy carbon electrode on the surface, and specifically comprises the following steps:
(1) preparing bismuth composite vermiculite loaded polyaniline carbide:
(1-1) pretreating vermiculite, namely sequentially carrying out water washing, acid washing, water washing and drying on 10g of 400-mesh vermiculite powder with the particle size of 200-;
(1-2) dissolving 0.1mol of aniline in 100ml of 2 mol/L hydrochloric acid solution, dispersing 2g of bismuth composite vermiculite powder in the solution, stirring the solution uniformly, adding 0.2mol of hydrogen peroxide into the solution, stirring the solution at 30 ℃ for reaction for 20 hours to obtain paste, removing the solvent of the paste, putting the paste in a tube furnace, introducing nitrogen for 30 minutes, heating the mixture to 300 ℃ at the speed of 6 ℃/min, roasting the mixture for 1 hour, heating the mixture to 600 ℃ for 1 hour, heating the mixture to 900 ℃ for roasting the mixture for 1 hour, and cooling the mixture to obtain bismuth composite vermiculite loaded carbonized polyaniline for later use;
(2) preparing a modified sodium alginate dispersion liquid:
taking 100g of 4wt% sodium alginate solution, dropwise adding 0.4g of pentaerythritol into the solution, stirring and dispersing the solution uniformly, dropwise adding 1.5g of aminopropyltrimethoxysilane into the solution under the stirring condition at 60 ℃, and reacting for 3 hours to obtain modified sodium alginate dispersion for later use;
(3) preparation of composite electrode
Grinding the vermiculite loaded carbonized polyaniline powder in the step (1), dispersing the grinded powder in the modified sodium alginate dispersion liquid in the step (2), coating the grinded powder on the surface of a polished glassy carbon electrode, immersing the coated glassy carbon electrode into 100m L0.5 mol/L calcium ion solution for crosslinking, and drying to obtain a bismuth composite vermiculite loaded carbonized polyaniline modified glassy carbon electrode;
comparative example 1
Preparing a bismuth composite polyaniline carbide modified glassy carbon electrode:
dissolving 0.05mol of aniline in 100ml of 1 mol/L hydrochloric acid solution, stirring uniformly, adding 0.1mol of hydrogen peroxide, stirring at 25 ℃ for reaction for 25 hours, adding 0.004mol of bismuth nitrate and 0.004mol of glucose, stirring until the bismuth nitrate and the glucose are completely dissolved to obtain a mixture, drying the mixture in a drying box to obtain a solid product, and roasting the solid product in a tubular furnace to obtain the bismuth composite carbonized polyaniline for later use, wherein the roasting process is the same as that in example 1;
preparing a bismuth composite polyaniline carbide modified glassy carbon electrode by adopting the same method as the steps (2) and (3) in the embodiment 1;
comparative example 2
Preparing a bismuth composite polyaniline carbide modified glassy carbon electrode: the preparation method is the same as that of example 1, except that the firing process in step (1-2) is: heating to 800 ℃ at the speed of 4 ℃/min, and roasting for 3-4h to obtain bismuth composite vermiculite loaded carbonized polyaniline for later use;
characterization and analysis of the bismuth composite vermiculite loaded polyaniline powder:
XRD analysis
The XRD analysis result of the bismuth composite vermiculite loaded with the carbonized polyaniline shows that: the characteristic peak of vermiculite appears in the range of 2-10 degrees; characteristic peaks of carbon-doped bismuth oxide appear at 25.1 °, 28.4 °, 32.3 °, 40.8 °, and 55.3 ° 2 θ.
And (3) analyzing the micro morphology:
the morphology of the bismuth composite vermiculite loaded carbonized polyaniline powder obtained by preparation is characterized and analyzed by using a field emission scanning electron microscope (JSM-7001F), and the result is shown in figure 1;
as can be seen from fig. 1, the carbon material with a network structure formed by carbonized polyaniline is loaded between vermiculite layers; granular bismuth oxide particles are also distributed among the layers, and the polyaniline carbide has a porous structure, so that the specific surface area of the material is increased, and the enrichment of heavy metals is facilitated; the bismuth oxide and the carbon material are uniformly distributed among the expansion layer structures of the vermiculite, so that the bismuth oxide particles and the carbon material can be effectively prevented from falling off; the stability and the longer service life of the electrode material are ensured.
Specific surface area analysis:
testing the specific surface area, the pore volume and the pore diameter of the bismuth composite vermiculite-loaded carbonized polyaniline powder prepared in the example 1 and the bismuth composite vermiculite-loaded carbonized polyaniline powder prepared in the comparative example 2 by using a specific surface and pore diameter analyzer (JW-BK 822); the test results are shown in fig. 2.
As can be seen from FIG. 2, N of the bismuth composite vermiculite supported polyaniline carbide powder in the example 1 and the comparative example 2 of the invention2The absorption and desorption curves are all IV type and H exists2The type hysteresis loop shows that the bismuth composite vermiculite loaded carbonized polyaniline powder has a mesoporous structure; the specific surface areas of the materials calculated by the BET method are 678m respectively2/g、386m2The active sites on the surface of the electrode can be increased, so that the enrichment of heavy metal ions and the electrochemical test are facilitated; however, the bismuth-loaded polyaniline carbide composite vermiculite prepared in example 1 has a larger specific surface area than comparative example 2, and probably because the uniform loading of the carbon material can be effectively controlled by controlling the roasting temperature in a gradient manner, the specific surface area of the material is reduced due to the fact that the carbon material is prevented from being excessively stacked;
electrochemical detection
An electrochemical detection method for heavy metal ions comprises the steps of taking a prepared bismuth composite vermiculite loaded polyaniline carbide modified glassy carbon composite electrode as a working electrode, taking a solution containing heavy metal ions as a working solution, and testing by adopting an anodic stripping voltammetry;
the glassy carbon electrode modified by bismuth composite vermiculite-loaded polyaniline carbide prepared in example 1 is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a platinum electrode is used as a counter electrode, acetic acid-sodium acetate with pH of 4.5 is used as a buffer solution, the enrichment potential is-1.2V, the enrichment time is 120s, lead and cadmium ion solutions with different concentrations are respectively measured (the concentrations of lead and cadmium ions are respectively 5 mu g/L, 10 mu g/L, 15 mu g/L0, 20 mu g/L1, 25 mu g/L, 30 mu g/L, 40 mu g/L, 50 mu g/L, 60 mu g/L, 70 mu g/L, 80 mu g/L, 90 mu g/L, 100 mu g/L, 110 mu g/636, 120 mu g/L, 130 mu g/L, 140 mu g/L, 150 mu g/6384, 160 mu g/4642, 170 mu g/4642 and the concentrations of lead and cadmium ion are recorded in a corresponding curve of a lead/L mu g/L and a peak value table.
Table 1.
| Ion concentration (μ g/L) | Pb2+Peak current of dissolution (μ A) | Cd2+Peak current of dissolution (μ A) |
| 5 | 0.387 | 0.272 |
| 10 | 0.808 | 0.541 |
| 15 | 1.123 | 0.610 |
| 20 | 1.351 | 0.779 |
| 25 | 1.680 | 1.008 |
| 30 | 2.000 | 1.007 |
| 40 | 2.800 | 1.655 |
| 50 | 3.200 | 1.593 |
| 60 | 3.870 | 2.341 |
| 70 | 4.500 | 2.269 |
| 80 | 5.140 | 2.807 |
| 90 | 5.772 | 3.145 |
| 100 | 6.406 | 3.283 |
| 110 | 7.040 | 3.921 |
| 120 | 7.780 | 4.259 |
| 130 | 8.304 | 4.290 |
| 140 | 8.740 | 4.835 |
| 150 | 9.880 | 5.373 |
| 160 | 10.670 | 5.511 |
| 170 | 11.000 | 5.649 |
| 180 | 11.900 | 6.387 |
And drawing a linear regression equation (shown in figure 3) according to the relation between the concentrations of the lead ions and the cadmium ions and the dissolution peak current, and calculating the concentrations of the lead ions and the cadmium ions in the solution to be detected according to the linear regression equation.
It can be seen from fig. 3 that the peak current and the lead ion concentration show good linear relationship when the lead ion concentration is in the range of 5 μ g/L-180 μ g/L, and the linear fitting equation is that I ═ 0.0755+0.0633C (correlation coefficient R)2＝0.9984)；
The peak of cadmium ion is 5 mug/L-180 mug/LThe current and the cadmium ion concentration present a good linear relation, and the linear fitting equation is as follows: i-0.1034 +0.0338C (correlation coefficient R)2＝0.9904)。
Taking the glassy carbon composite electrode modified by bismuth composite polyaniline carbide obtained in the comparative example 1 as a working electrode, a saturated calomel electrode as a reference electrode, a platinum electrode as a counter electrode, acetic acid-sodium acetate with the pH value of 4.5 as a buffer solution, the enrichment potential of-1.2V, the enrichment time of 120s, lead and cadmium ion solutions with different concentrations (the concentrations of lead and cadmium ions are respectively 1 mu g/L, 5 mu g/L, 10 mu g/L0, 15 mu g/L1, 20 mu g/L2, 25 mu g/L, 30 mu g/L, 40 mu g/L, 50 mu g/L6, 60 mu g/L, 70 mu g/7378, 80 mu g/L, 90 mu g/L, 100 mu g/L, 110 mu g/L, 120 mu g/L, 130 mu g/L, 140 mu g/46150 mu g/L, 140 mu g/5842 and 57324 mu g/L mu g/170 mu g/3623, respectively) as a dissolution curve;
the detection result shows that lead ions show obvious peak current (0.35 muA) when the concentration is 15 mug/L, the peak current is weaker than that of example 1, cadmium ions show obvious peak current (0.27 muA) when the concentration is 30 mug/L, the peak current is weaker than that of example 1, the bismuth composite vermiculite loaded polyaniline carbide electrode material shows higher sensitivity because the layered structure of vermiculite improves the contact area of the electrode material and heavy metals, so that the adsorption capacity of the electrode material to the heavy metals is improved, the vermiculite is used as a load carrier to effectively reduce the agglomeration phenomenon of the bismuth oxide and the carbon material, the dispersibility of the bismuth oxide and the carbon material on a substrate is improved, on one hand, the electrode material keeps good conductivity, on the other hand, the active sites on the surface of the electrode are increased, so that the heavy metals are easier to be enriched on the surface of the electrode, and the detection sensitivity is improved;
reproducibility and stability of the electrode:
the composite electrode (10 pieces, numbered 1-10) prepared by the method of example 2 was used as a working electrode, a saturated calomel electrode was used as a reference electrode, a platinum electrode was used as a counter electrode, acetic acid-sodium acetate with pH of 4.5 was used as a buffer solution, the enrichment potential was-1.2V, the enrichment time was 120s, and the concentration time was 25. mu.g/L Pb2+And Cd2+The solutions were tested in parallel under the same conditions and the dissolution peak test data are shown in table 2.
TABLE 2 reproducibility examination of electrodes
| Electrode numbering | Pb2+Peak current of dissolution (μ A) | Cd2+Peak current of dissolution (μ A) |
| 1 | 1.658 | 0.987 |
| 2 | 1.674 | 0.964 |
| 3 | 1.634 | 0.967 |
| 4 | 1.673 | 0.956 |
| 5 | 1.706 | 0.945 |
| 6 | 1.696 | 0.977 |
| 7 | 1.692 | 1.005 |
| 8 | 1.645 | 1.078 |
| 9 | 1.618 | 0.976 |
| 10 | 1.675 | 1.041 |
| Relative Standard Deviation (SD) | 2.8％ | 4.1％ |
As can be seen from Table 2, Pb2+And Cd2+The relative standard deviation of detection is 2.8% and 4.1% respectively, which shows that the prepared electrode has good reproducibility;
drying the used No. 1-10 electrodes after being placed at normal temperature for 15 days, and then treating the electrode with 25 mu g/L Pb2+And Cd2+Measuring the solution; the test results showed that 10 electrodes tested to obtain Pb2+And Cd2+The change value (average value) of the dissolution peak current of (2) is less than 5%, which shows that the prepared electrode has good stability.
In conclusion, the composite electrode prepared by the invention has good stability and reproducibility, and can be simultaneously used for detecting heavy metal lead and cadmium ions; under the optimized test condition, the kit has high detection sensitivity, wide detection range and low detection limit on lead and cadmium ions.
Finally, the above embodiments are only used for illustrating the technical solution of the present invention and not for limiting, and other modifications or equivalent substitutions made by the technical solution of the present invention by those skilled in the art should be covered within the scope of the claims of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
1. The composite electrode for detecting heavy metal ions is characterized by being prepared by taking bismuth composite vermiculite loaded polyaniline carbide as a modifier and modified sodium alginate as a film-forming agent to modify a glassy carbon electrode, and specifically comprises the following steps:
(1) preparing bismuth composite vermiculite loaded polyaniline carbide:
pretreating vermiculite: the vermiculite powder is soaked in bismuth salt reducing sugar solution for ultrasonic treatment for 12 to 14 hours after being washed with water, acid, water and dried in sequence; filtering and drying to obtain bismuth composite vermiculite;
(1-2) dissolving aniline in an acid solution to form an acid solution of aniline, dispersing the bismuth composite vermiculite powder in the step (1-1) in the acid solution, uniformly stirring, adding hydrogen peroxide into the acid solution, stirring and reacting at 25-30 ℃ for 20-25 hours to obtain paste, removing the solvent from the paste, and placing the paste in a tubular furnace to roast to obtain bismuth composite vermiculite loaded carbonized polyaniline;
(2) preparing a modified sodium alginate dispersion liquid:
adding polyol into a sodium alginate solution, stirring and dispersing uniformly, then dropwise adding a silane coupling agent into the solution under the stirring condition of 50-60 ℃, and reacting for 3-5 hours to obtain a modified sodium alginate dispersion solution for later use;
(3) preparation of working electrode
Grinding the vermiculite loaded polyaniline carbide powder in the step (1), dispersing the grinded powder in the modified sodium alginate dispersion liquid in the step (2), coating the grinded powder on the surface of the glassy carbon electrode, immersing the coated glassy carbon electrode into a calcium ion solution for crosslinking, and drying to obtain the bismuth composite vermiculite loaded polyaniline carbide modified glassy carbon electrode.
2. The composite electrode for detecting heavy metal ions according to claim 1, wherein the particle size of the vermiculite powder in the step (1-1) is 200-400 meshes, and the acid washing is performed by soaking the vermiculite in 5 mol/L HCl solution 2-5 times of the weight of the vermiculite.
3. The composite electrode for detecting heavy metal ions according to claim 1, wherein the bismuth salt in the step (1-1) is one of bismuth nitrate, bismuth acetate and bismuth chloride, the molar concentration of the bismuth salt in the bismuth salt reducing sugar solution is 0.02-0.04 mol/L, the molar ratio of the bismuth salt to the reducing sugar is 1: 1, and the addition amount of the bismuth salt solution is 2-4 times of the weight of the vermiculite.
4. The composite electrode for detecting heavy metal ions according to claim 1, wherein the acid in the step (1-2) is hydrochloric acid or sulfuric acid, and the concentration of the acid solution is 1-2 mol/L.
5. The composite electrode for heavy metal ion detection according to claim 1, wherein the concentration of aniline in the acid solution in step (1-2) is 0.5-1 mol/L, the mass ratio of the added vermiculite powder to the aniline acid solution is 1: 10-20, and the molar ratio of aniline to hydrogen peroxide is 1: 2-2: 1.
6. The composite electrode for detecting heavy metal ions according to claim 1, wherein the roasting process in the step (1-2) is performed in three stages, the roasting temperature in the first stage is 200-300 ℃, and the roasting time is 1-2 h; the second stage is roasting at 600 ℃ for 1-2h, the third stage is roasting at 900 ℃ for 1-2h, and the temperature rise speed is controlled at 4-6 ℃/min.
7. The composite electrode for detecting heavy metal ions according to claim 1, wherein the concentration of sodium alginate in the step (2) is 1wt% to 4wt%, the polyol is pentaerythritol, and the addition amount of the pentaerythritol is 8 wt% to 10 wt% of the weight of the sodium alginate; the adding amount of the silane coupling agent is 10-15% of the mass of the sodium alginate; the silane coupling agent is an amino silane coupling agent.
8. The method for detecting the concentration of the heavy metal ions by using the composite electrode for detecting the heavy metal ions as claimed in claim 1, is characterized in that the bismuth composite vermiculite loaded polyaniline carbide modified glassy carbon electrode is used as a working electrode, a solution containing the heavy metal ions is used as a working solution, an anodic stripping voltammetry is adopted for testing, a linear regression equation is constructed according to the relation between the concentration of the metal ions and peak current, and the concentration of the heavy metal ions in the solution to be tested is calculated.
9. The method according to claim 8, wherein the heavy metal ions are lead ions and/or cadmium ions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010389232.6A CN111398385B (en) | 2020-05-10 | 2020-05-10 | Composite electrode for heavy metal ion detection and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010389232.6A CN111398385B (en) | 2020-05-10 | 2020-05-10 | Composite electrode for heavy metal ion detection and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111398385A true CN111398385A (en) | 2020-07-10 |
| CN111398385B CN111398385B (en) | 2023-12-29 |
Family
ID=71433683
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010389232.6A Active CN111398385B (en) | 2020-05-10 | 2020-05-10 | Composite electrode for heavy metal ion detection and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111398385B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113702456A (en) * | 2021-04-30 | 2021-11-26 | 广州钰芯智能科技研究院有限公司 | Bismuth film modified electrode for heavy metal detection and preparation method thereof |
| CN114113249A (en) * | 2021-11-25 | 2022-03-01 | 浙江大学 | Heavy metal extraction and detection method for infant milk powder |
| CN116399923A (en) * | 2023-03-07 | 2023-07-07 | 兰州大学 | Nanometer bismuth oxide embedded nitrogen-doped carbon nano sheet composite material and electrochemical method for detecting heavy metal by using same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102247830A (en) * | 2011-05-17 | 2011-11-23 | 东华大学 | Preparation method of vermiculite self-assembly bismuth vanadate water treatment agent |
| CN103433077A (en) * | 2013-09-11 | 2013-12-11 | 江南大学 | Three-element composite photocatalyst and preparation method thereof |
| CN110665517A (en) * | 2019-08-02 | 2020-01-10 | 南京理工大学 | Composite material prepared by carrying bismuth molybdate and cadmium sulfide on phlogopite/ZnO for concerted catalysis and preparation method thereof |
-
2020
- 2020-05-10 CN CN202010389232.6A patent/CN111398385B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102247830A (en) * | 2011-05-17 | 2011-11-23 | 东华大学 | Preparation method of vermiculite self-assembly bismuth vanadate water treatment agent |
| CN103433077A (en) * | 2013-09-11 | 2013-12-11 | 江南大学 | Three-element composite photocatalyst and preparation method thereof |
| CN110665517A (en) * | 2019-08-02 | 2020-01-10 | 南京理工大学 | Composite material prepared by carrying bismuth molybdate and cadmium sulfide on phlogopite/ZnO for concerted catalysis and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| DAOFU LIU等: "Facile synthesis of exfoliated polyaniline/vermiculite nanocomposites", 《MATERIALS LETTERS》 * |
| KATERYNA RYABCHENKO等: "Adsorption Properties of Bentonite with In Situ Immobilized Polyaniline Towards Anionic Forms of Cr(VI), Mo(VI), W(VI), V(V)", 《MATERIALS SCIENCE》 * |
| XIN-HUANG等: "Hydrochlorination of acetylene using expanded multilayered vermiculite (EML-VMT)-supported catalysts" * |
| Z. M. WANG等: "Bismuth/Polyaniline/Glassy Carbon Electrodes Prepared with", 《ELECTROANALYSIS》 * |
| ZHAOBIN TANG等: "Preparation of polyaniline/vermiculite clay", 《POLYM INT》 * |
| ZHAOMENG WANG等: "Graphene ultrathin film electrodes modified with bismuth nanoparticles", 《THIN SOLID FILMS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113702456A (en) * | 2021-04-30 | 2021-11-26 | 广州钰芯智能科技研究院有限公司 | Bismuth film modified electrode for heavy metal detection and preparation method thereof |
| CN113702456B (en) * | 2021-04-30 | 2024-03-26 | 广州钰芯智能科技研究院有限公司 | Bismuth film modified electrode for heavy metal detection and preparation method thereof |
| CN114113249A (en) * | 2021-11-25 | 2022-03-01 | 浙江大学 | Heavy metal extraction and detection method for infant milk powder |
| CN116399923A (en) * | 2023-03-07 | 2023-07-07 | 兰州大学 | Nanometer bismuth oxide embedded nitrogen-doped carbon nano sheet composite material and electrochemical method for detecting heavy metal by using same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111398385B (en) | 2023-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111398385A (en) | Composite electrode for heavy metal ion detection and preparation method thereof | |
| CN109651621B (en) | Zirconium-based metal organic framework composite material and preparation method and application thereof | |
| CN110064368B (en) | Preparation method of silicon-manganese modified biochar composite material | |
| CN109678137B (en) | Preparation method of hollow carbon nanospheres | |
| CN109065371B (en) | Flexible electrode and preparation method and application thereof | |
| CN108414589A (en) | Foam-like porous carbon net/nickel nano particle three-dimensional composite and its synthetic method and application | |
| CN110993368A (en) | Composite electrode material, preparation method and super capacitor | |
| CN111424339A (en) | Transition metal oxide-loaded porous carbon fiber, biosensor and preparation method thereof | |
| CN113588751B (en) | MXene@CoAl-LDH nano composite membrane modified electrode, preparation method thereof and application of modified electrode in pesticide detection | |
| CN114538409A (en) | Preparation method and application of nitrogen-doped carbon dot-reduced graphene oxide composite material | |
| CN111440328A (en) | Boric acid modified metal oxide nano array-MOF composite material, and preparation method and application thereof | |
| Zhu et al. | Rapid fabrication of electrode for the detection of alpha fetoprotein based on MnO2 functionalized mesoporous carbon hollow sphere | |
| CN107328834B (en) | Composite material modified electrode for detecting lead ions in livestock and poultry drinking water and preparation method thereof | |
| CN113311043A (en) | Detect Pb2+And Hg2+Electrochemical sensor and preparation method and application thereof | |
| CN113777144A (en) | Electrochemical sensor for detecting dopamine in gastric juice and preparation method and application thereof | |
| CN105529194B (en) | A kind of MnO2@graphene capsule@MnO2The preparation method of composite | |
| CN109585181A (en) | The preparation method of storage lithium nitrating porous carbon positive electrode based on brown alga egg-box structure | |
| CN108760843B (en) | Method for preparing electrochemical sensor for hydrogen peroxide detection from shaddock peel | |
| CN111398384B (en) | Copper ion detection electrochemical sensor | |
| CN114852995B (en) | Electrocatalytic application of horseradish peroxidase sensor constructed by black phosphorus-based composite material | |
| CN114538530A (en) | Basic cobalt carbonate nano material for electrochemical sensor and preparation method and application thereof | |
| CN111999358A (en) | Application of graphite-like phase carbon nitride nano material as electrochemical modified electrode material in methyl mercury detection | |
| CN114984926A (en) | Preparation method of high-agglomeration-resistance RGO-based magnetic lithium ion imprinted polymer | |
| CN114561020B (en) | Metal-organic framework-Cu nano material for electrochemical sensor and preparation method and application thereof | |
| CN110927234B (en) | Nano material compound, processing method thereof and application thereof in tumor cell detection |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20231128 Address after: Room 202, 2nd Floor, Building 56, No. 21 North Hongluo East Road, Dazhong Fule Village, Huairou District, Beijing, 101400 Applicant after: Beijing Huaisheng High tech Industry Development Co.,Ltd. Address before: 450000 Zhengzhou new material industrial park, No. 9, Yinping Road, Zhongyuan District, Zhengzhou City, Henan Province Applicant before: Chen Xianli |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |